Multilayer films for insert mold decoration, methods for making the same, and articles made therefrom

ABSTRACT

A multilayer thermoplastic film having polycarbonate layers is disclosed, in which a first layer comprises a first polycarbonate that comprises repeat units derived from one or more of a monoaryl monomer (II) and/or (III), and a diaryl monomer (IV) as defined herein. A second layer, adjacent to the first layer and coextruded therewith, comprises another polycarbonate that is not the same as a polycarbonate in the first layer. The first layer provides improved properties, for example hardness, impact, and/or scratch resistance.

BACKGROUND OF THE INVENTION

This disclosure relates to compositions for the manufacture ofmultilayer thermoplastic films, methods for the manufacture of themultilayer thermoplastic films, and articles made with the multilayerthermoplastic films. The multilayer thermoplastic films are especiallyuseful for in-mold decoration.

Decorating a three-dimensional article via in-mold decoration (IMD),also known as insert mold decoration, involves inserting a decorativefilm (often referred to as a substrate) into a molding tool; andinjecting a molten base polymer behind it in an injection molding cycle.The decorative film is bonded with or encapsulated by the molten basepolymer, to provide an injection molded article or finished part havingthe desired decoration after the injection molding cycle is complete.Thus, the decorative film becomes a permanent fixture of the finishedpart. The decoration for the finished part can either be exposed to theenvironment as “first surface decoration” and/or encapsulated betweenthe substrate of the decorative film and the injected material as“second surface decoration.”

The term “decorative film” as used herein refers to a film havingsurface printing or other marking of an aesthetic, functional, and/orinformational nature including, for example, symbols, logos, designs,colored regions, and/or alphanumeric characters. When printed with ink,formable and high temperature inks are generally used. The decorativefilm can also act as an aesthetic effect carrier and/or as a protectivelayer for the base polymer, the ink used to mark the film, or both. Whenused to manufacture a three-dimensional article, decorative films areoften thermoformed on a tool into a three-dimensional shape thatcorresponds to the three-dimensional shape desired for the injectionmolded article.

Processes for making decorative film are disclosed in U.S. Pat. No.6,117,384 to Laurin et al., which describes a process wherein a coloreddecorated film is incorporated with a molten polymer injected behind thefilm to produce a permanently bonded three-dimensional piece. U.S. Pat.No. 6,458,913 to Honigfort and U.S. Pat. No. 6,682,805 to Lilly alsodescribe insert mold decorative films and articles. Lilly describes amultilayer thermoplastic printable film comprising a thermoplastic filmsubstrate having laminated to one surface a fluoride polymer in order toimprove the birefringence and other properties of the film, includingchemical resistance.

Polycarbonates are especially useful thermoplastic materials for themanufacture of decorative films, based at least in part on theirhardness and processability. Polycarbonate films can also bemanufactured to have high transparency, which is advantageous indecorative films.

Despite their wide use, there remains a perceived need in the art forimproved polycarbonate compositions for use in the manufacture ofdecorative films, as well as decorative films with improved properties.For example, there remains a need in the art for polycarbonatecompositions and decorative films where the exposed surface of thedecorative film has improved scratch and/or chemical resistance.

SUMMARY OF INVENTION

A multilayer thermoplastic film comprises a first layer comprising afirst polycarbonate that comprises repeat units derived from monomers(II), (III), and (IV), wherein monomer (II) is a first dihydroxycompound of the formula:

wherein n is 0 to 4, and R^(f1) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group; monomer (III) is asecond dihydroxy compound not the same as monomer (II) and of theformula:

wherein m is 1 to 4, and R^(f2) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group; and monomer (IV) is athird dihydroxy compound of the formula:

wherein R^(a) and R^(b) are each independently a halogen or C₁₋₁₂ alkylgroup; R^(c) and R^(d) each independently represent a C₁-C₁₂ alkyl; pand q are each independently integers of 0 to 4; v and w are eachindependently integers 0 to 2; and X^(a) is a single bond or a bridginggroup; wherein the sum of the mole percent of the repeat units derivedfrom monomers (II) and (III) is greater than or equal to 30 molepercent, based on the total moles of the repeat units derived frommonomers (II), (III), and (IV) in the first polycarbonate; the molepercent of the repeat units derived from monomer (IV) is 5 to 70 molepercent, based on the total moles the repeat units derived from monomers(II), (III), and (IV); and the total wt. % of the repeat units derivedfrom monomers (II), (III), and (IV) is greater than or equal to 80 wt. %of the first polycarbonate; and a second layer adjacent to the firstlayer, wherein the second layer comprises a second polycarbonate that isnot the same as the first polycarbonate in the first layer.

In another embodiment, a multilayer thermoplastic film comprises a firstpolycarbonate and an additional polycarbonate that is not the same asthe first polycarbonate, wherein the additional polycarbonate comprises50 to 100 mole percent of repeat units derived from a bisphenolcyclohexane of the formula (VI):

wherein R^(c1) and R^(d1) are each independently C₁₋₁₂ alkyl, R^(c2) andR^(d2) are each independently hydrogen or C₁₋₁₂ alkyl, R^(g) is C₁₋₁₂alkyl or halogen, and t is 0 to 10; 0 to 50 mole percent of repeat unitsderived from a dihydroxy aromatic compound of formula (VIII):

wherein R^(e) and R^(f) are each independently a halogen or C₁₋₁₀ alkylgroup; r and s are each independently integers of 0 to 4; X^(a) is asingle bond or a bridging group connecting the two hydroxy-substitutedaromatic groups; and the dihydroxy aromatic compound of formula (VIII)is not the same as the bisphenol cyclohexylidene of formula (VI).

In another embodiment, a method for the manufacture of a multilayerthermoplastic film comprises coextruding the aforementioned first andsecond layers.

In another embodiment, an article comprises the aforementionedmultilayer thermoplastic film, and further optionally comprises aprinted marking in combination with an injection molded polymeric baseto which the film is bonded.

In still another embodiment, a method of molding an article comprisesplacing the multilayer thermoplastic film into a mold, and injecting abase polymer into a mold cavity space behind the multilayer to form asingle molded part comprising the multilayer film and the injectionmolded base resin.

DETAILED DESCRIPTION OF THE INVENTION

The inventors hereof have unexpectedly found that multilayer decorativefilms having an excellent combination of properties, including impactproperties and chemical resistance, can be achieved using twopolycarbonate layers. The polycarbonate in the first layer comprises aspecific combination of at least three different repeat units. Anexcellent combination of scratch, impact performance and chemicalresistance is obtained when at least a portion of the repeat units arederived from a bisphenol cyclohexylidene, as described in further detailbelow.

Unexpectedly, it has also been found that an excellent combination ofscratch, impact performance and chemical resistance is obtained when thefirst layer comprises a blend of at least two polycarbonates: thepolycarbonate having the combination of at least three different repeatunits; and an additional polycarbonate having repeat units derived fromthe bisphenol cyclohexane. A method of forming these polycarbonateblends comprises melt blending a first polycarbonate comprising aspecific combination of at least three different repeat units; and anadditional polycarbonate comprising repeat units derived from abisphenol cyclohexylidene, optionally in the presence of a catalyst.

“Polycarbonates” as used herein generally means compositions havingrepeating structural carbonate units of formula (I):

wherein R¹ is a residue derived from a dihydroxy compound of the formulaHO—R¹—OH or chemical equivalent thereof. The multilayer thermoplasticfilm disclosed herein comprises a first polycarbonate that comprisesrepeat units derived from three different dihydroxy monomers (II),(III), and (IV), each as described below.

Monomer (II) is a first dihydroxy compound of the formula (II):

wherein n is 0 to 4, and R^(f1) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group. Specifically, n is 0to 2, and R^(f1) is a halogen, a C₁₋₃ hydrocarbon group, or a C₁₋₃halogen-substituted hydrocarbon group. More specifically, n is 0 to 1,R^(f1) is a halogen, a C₁₋₃ alkyl group, or a C₁₋₃ halogen-substitutedalkyl group, and the hydroxy groups are in the para position relative toeach other. Even more specifically, monomer (II) is hydroquinone,wherein n is 0 and the hydroxy groups are in the para position relativeto each other.

Monomer (III) is a second dihydroxy compound that is not the same asmonomer (II), and is of the formula (III):

wherein m is 1 to 4, and R^(f2) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group. Specifically, m is 1to 2, and R^(f2) is a halogen, a C₁₋₃ hydrocarbon group, or a C₁₋₃halogen-substituted hydrocarbon group. More specifically, m is 1, andR^(f2) is a halogen, a C₁₋₃ alkyl group, or a C₁₋₃ halogen-substitutedalkyl group, and the hydroxy groups are in the meta position relative toeach other. Even more specifically, monomer (III) is methylhydroquinone, wherein m is 1, R^(f2) is methyl, and the hydroxy groupsare in the para position relative to each other.

As shown in the Examples, a polycarbonate comprising units derived froma combination of hydroquinone (monomer (II)) and methyl hydroquinone(monomer (III)) provides good results.

Monomer (IV) is a dihydroxy compound of the formula (IV):

wherein R^(a) and R^(b) are each independently a halogen or C₁₋₁₀ alkylgroup that is meta to the hydroxy group on the same aromatic ring; R^(c)and R^(d) are each independently a C₁-C₁₀ alkyl group that is ortho tothe hydroxy group on the same ring; p and q are each independentlyintegers of 0 to 2; v and w are each independently integers of 0 to 2;and X^(a) is a single bond or a bridging group, specifically a singlebond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic groupconnecting the two hydroxy-substituted aromatic groups.

Specifically, X^(a) in monomer (IV) can be a C₁₋₁₂ organic group. Morespecifically, the C₁₋₁₂ organic group can be disposed such that thehydroxy-substituted aromatic groups connected thereto are each connectedto a common alkylidene carbon in X^(a). Further, X^(a) can be asubstituted or unsubstituted C₃₋₁₈ cycloalkylidene, a C₁₋₂₄ alkylideneof formula —C(R^(j))(R^(k))— wherein R^(j) and R^(k) are eachindependently hydrogen, C₁₋₁₂ alkyl, C₃₋₁₂ cycloalkyl, C₇₋₁₂ arylalkyl,C₁₋₁₂ heteroalkyl, cyclic C₇₋₁₂ heteroarylalkyl, or a group of theformula —(═R^(m))— wherein R^(m) is a divalent C₁₋₁₂ hydrocarbon group.In a specific embodiment, X^(a) is a C₁₋₈ alkylidene or cycloalkylidenegroup.

In another specific embodiment, R^(a) and R^(b) are each independently ahalogen or C₁₋₃ alkyl group that is meta to the hydroxy group on thesame aromatic ring; R^(c) and R^(d) are each independently a C₁₋₃ alkylgroup that is ortho to the hydroxy group on the same ring; p and q areeach independently integers of 0 to 1; v and w are each independentlyintegers of 0 to 2; and X^(a) is a C₁₋₈ alkylidene or cycloalkylidenegroup.

The relative amounts of each of the units derived from monomers (II),(III), and (IV) in the first polycarbonate will depend on the desiredproperties of the multilayer film, as well as the properties of thesecond polycarbonate layer. It has been found that a combination of goodscratch resistance and/or impact performance and chemical resistance isachieved when the sum of the mole percent of the repeat units derivedfrom monomers (II) and (III) is greater than or equal to 30 molepercent, specifically 35 to 60 mole percent, more specifically 40 to 70mole percent, each based on the total moles of the repeat units derivedfrom monomers (II), (III), and (IV) in the first polycarbonate; and themole percent of the repeat unit derived from monomer (IV) is 5 to 70mole percent, specifically 10 to 60 mole percent, more specifically 20to 50 mole percent, each based on the on the total moles the repeatunits derived from monomers (II), (III), and (IV) in the firstpolycarbonate. Further, the total weight of the repeat units derivedfrom monomers (II), (III), and (IV) is greater than or equal to 90weight percent (wt. %) of the first polycarbonate. The ratio of the molepercent of repeat units derived from monomer (II):monomer (III) can be1:99 to 99:1, specifically 10:90 to 90:10.

In another specific embodiment, monomer (IV) is of the formula (V):

wherein R^(a) and R^(b) are each independently a halogen or C₁₋₁₀ alkylgroup that is meta to the hydroxy group on the same aromatic ring; p andq are each independently integers of 0 to 2; and the bridging groupX^(b) is a C₁₋₈ alkylidene of formula —C(R^(j))(R^(k))— wherein R^(j)and R^(k) are each independently hydrogen or C₁₋₄ alkyl. Specifically,in formula (V), R^(a) and R^(b) are each methyl, p and q are each 1, andX^(b) is isopropylidene. Alternatively, monomer (V) is bisphenol A,wherein q and p are each 0 and X^(b) is isopropylidene.

Alternatively, monomer (IV) can be a bisphenol cyclohexylidene in whichp and q are each 0, R^(c) and R^(d) are each a C₁₋₄ alkyl group, v and ware each 1 or 2, specifically 2, and X^(a) is substituted orunsubstituted cyclohexylidene. In this embodiment, monomer (IV) is abisphenol cyclohexylidene of the formula (VI):

wherein R^(c1) and R^(d1) are each independently C₁₋₁₂ alkyl, R^(c2) andR^(d2) are each independently hydrogen or C₁₋₁₂ alkyl, R^(g) is C₁₋₁₂alkyl or halogen, and t is 0 to 10.

More specifically, in structure (VI), R^(c1) and R^(d1) are eachindependently C₁₋₄ alkyl, R^(c2) and R^(d2) are each hydrogen, R^(g) isC₁₋₄ alkyl, and t is 0 to 5. Still more specifically, monomer (VI) is abisphenol cyclohexylidene wherein R^(c1) and R^(d1) are each methyl,R^(c1) and R^(d1) are each hydrogen, and t is 0, i.e., a monomer offormula (VII):

which is also known as dimethyl bisphenol cyclohexane (DMBPC).

Thus, monomer (IV) can be 100 mole percent monomer (V), specificallybisphenol A, or 100 mole percent monomer (VI), specifically monomer(VII). In still another embodiment, monomer (IV) is a combination of twodifferent types of compounds: a bisphenol cyclohexylidene of formula(VI), specifically formula (VII), and a monomer of formula (IV) that isnot the same as the bisphenol cyclohexylidene of formula (VI), forexample a monomer of formula (IV) wherein R^(a) and R^(b) are eachindependently a halogen or C₁₋₁₀ alkyl group that is meta to the hydroxygroup on the same aromatic ring; R^(c) and R^(d) are each independentlya C₁-C₁₀ alkyl group that is ortho to the hydroxy group on the samering; p and q are each independently integers of 0 to 2; v and w areeach independently integers of 0 to 2; and X^(a) is a single bond, —O—,—S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₈ alkylidene of formula—C(R^(j))(R^(k))— wherein R^(j) and R^(k) are each independentlyhydrogen or C₁₋₄ alkyl.

In this embodiment, monomer (IV) is 1 to 99 mole percent of a bisphenolcyclohexylidene of formula (VI), specifically formula (VII), and 1 to 99mole percent of a monomer of formula (IV) that is not the same as thebisphenol cyclohexylidene of formula (VI). More specifically, monomer(IV) is 20 to 80 mole percent of a bisphenol cyclohexylidene of formula(VI), specifically formula (VII), and 20 to 80 mole percent of a monomerof formula (IV) that is not the same as the bisphenol cyclohexylidene offormula (VI). Even more specifically, monomer (IV) comprises 40 to 60mole percent of a bisphenol cyclohexylidene of formula (VI),specifically formula (VII), and 40 to 60 mole percent of a monomer offormula (IV) that is not the same as the bisphenol cyclohexylidene offormula (VI).

In still another embodiment, monomer (IV) is a combination of abisphenol cyclohexylidene of formula (VI), specifically formula (VII),and a monomer of formula (V), specifically bisphenol A. In thisembodiment, monomer (IV) is 1 to 99 mole percent of a bisphenolcyclohexylidene of formula (VI), specifically formula (VII), and 1 to 99mole percent of a monomer of formula (V), specifically bisphenol A. Morespecifically, monomer (IV) is 20 to 80 mole percent of a bisphenolcyclohexylidene of formula (VI), specifically formula (VII), and 20 to80 mole percent of a monomer of formula (V), specifically bisphenol A.Even more specifically, monomer (IV) is 40 to 60 mole percent of abisphenol cyclohexylidene of formula (VI), specifically formula (VII),and 40 to 60 mole percent of a monomer of formula (V), specificallybisphenol A.

Polycarbonates comprising repeat units derived from the foregoingmonomers (II), (III), and (IV) can be manufactured by processes such asinterfacial polymerization and melt polymerization. Although thereaction conditions for interfacial polymerization may vary, anexemplary process generally involves dissolving or dispersing thedihydroxy monomers in aqueous caustic sodium hydroxide or potassiumhydroxide, adding the resulting mixture to a suitable water-immisciblesolvent (e.g., methylene chloride, 1,2-dichloroethane, chlorobenzene,toluene, or the like), and contacting the reactants with a carbonateprecursor (e.g., carbonyl chloride, or a haloformate such as abishaloformate of the monomer) in the presence of a catalyst such astriethylamine or a phase transfer catalyst, under controlled pHconditions, e.g., about 8 to about 10. Among the phase transfercatalysts that can be used are catalysts of the formula (R³)₄Q⁺X⁻,wherein each R³is the same or different, and is a C₁₋₁₀ alkyl group; Qis a nitrogen or phosphorus atom; and X is an inorganic or C₁₋₂₀ organicanion, in particular a halogen atom, a C₁₋₈ alkoxy group, or a C₆₋₁₈aryloxy group. Useful phase transfer catalysts include, for example,[CH₃(CH₂)₃]₄N⁺X⁻, [CH₃(CH₂)₃]₄P⁺X⁻, [CH₃(CH₂)₅]₄N⁺X⁻, [CH₃(CH₂)₆]₄N⁺X⁻,[CH₃(CH₂)₄]₄NX⁻, CH₃[CH₃(CH₂)₃]₃N⁺X⁻, and CH₃[CH₃(CH₂)₂]₃N⁺X⁻, wherein Xis Cl⁻, Br⁻, a C₁₋₈ alkoxy group or a C₆₋₁₈ aryloxy group.

Alternatively, melt processes can be used to make the polycarbonates.Generally, in the melt polymerization process, polycarbonates areprepared by co-reacting, in a molten state, the dihydroxy monomers and adiaryl carbonate ester in the presence of a catalyst in a Banbury®mixer, twin screw extruder, or the like to form a uniform dispersion.Volatile monohydric phenol is removed from the molten reactants bydistillation and the polymer is isolated as a molten residue. Catalystsinclude phase transfer catalysts of formula (R³)₄Q⁺X⁻ above, whereineach of R³, Q, and X are as defined above.

Branched polycarbonate blocks can also be used and can be prepared byadding a branching agent during polymerization. These branching agentsinclude polyfunctional organic compounds containing at least threefunctional groups selected from hydroxyl, carboxyl, carboxylicanhydride, haloformyl, and mixtures of the foregoing functional groups.Specific examples include trimellitic acid, trimellitic anhydride,trimellitic trichloride, tris-p-hydroxy phenyl ethane (THPE),isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents can be added ata level of 0.05 to 2.0 wt. %. Mixtures comprising linear polycarbonatesand branched polycarbonates can be used.

A chain stopper (also referred to as a capping agent) can be includedduring polymerization. The chain stopper limits molecular weight growthrate, and so controls molecular weight in the polycarbonate. Exemplarychain stoppers include certain mono-phenolic compounds, mono-carboxylicacid chlorides, and/or mono-chloroformates.

The polycarbonates containing repeat units derived from monomers (II),(III), and (IV) can have an intrinsic viscosity, as determined inchloroform at 25° C., of 0.3 to 1.5 deciliters per gram (dl/gm),specifically 0.45 to 1.0 dl/gm. The polycarbonates can have a weightaverage molecular weight (Mw) of 10,000 to 200,000 Daltons, specifically20,000 to 100,000 Daltons, as measured by GPC, using a crosslinkedstyrene-divinylbenzene column and calibrated to polycarbonatereferences. GPC samples are prepared at a concentration of 1 mg per mland are eluted at a flow rate of 1.5 ml per minute. In one embodiment,the polycarbonate is amorphous.

The first layer can comprise a single polycarbonate as described above(“first polycarbonate”). For example, in one embodiment, the first layercomprises a first polycarbonate comprising units derived from monomer(II), monomer (III), and a bisphenol cyclohexylidene of formula (VI),specifically of formula (VII). The Examples show that a good combinationof properties is obtained when the first polycarbonate comprises unitsderived from hydroquinone, methyl hydroquinone, and dimethyl bisphenolcyclohexane. No other polymer is present in the first layer.

Alternatively, the first layer can comprise a blend comprising a firstpolycarbonate as described above and an additional polycarbonatedifferent from the first polycarbonate. The additional polycarbonatecomprises greater than or equal to 50 mole percent of repeat unitsderived from the bisphenol cyclohexylidene of formula (VI), specificallyformula (VII), based on the total weight of the additionalpolycarbonate. Other repeat units that can optionally be present in theadditional polycarbonate are different from the bisphenolcyclohexylidene of formula (VI), and are derived from a dihydroxyaromatic compound of formula (VIII):

wherein R^(e) and R^(f) are each independently a halogen or C₁₋₁₀ alkylgroup; r and s are each independently integers of 0 to 4; and X^(a) is asingle bond or a bridging group connecting the two hydroxy-substitutedaromatic groups, where the single bond or the bridging group and thehydroxy substituent of each C₆ arylene group are disposed ortho, meta,or para (specifically para) to each other on the C₆ arylene group. In anembodiment, X^(a) is a single bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—,or a C₁₋₁₈ organic group. The C₁₋₁₈ organic group can be cyclic oracyclic, aromatic or non-aromatic, and can further comprise heteroatomssuch as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. TheC₁₋₁₈ organic group can be disposed such that the C₆ arylene groupsconnected thereto are each connected to a common alkylidene carbon or todifferent carbons of the C₁₋₁₈ organic group. Specifically, X^(a) can bea C₁₋₈ alkylidene bridging group of the formula —C(R^(j))(R^(k))—wherein R^(j) and R^(k) are each independently hydrogen or C₁₋₄ alkyl.In one embodiment, r and s is each 1, and R^(a) and R^(b) are each aC₁₋₃ alkyl group, specifically methyl, disposed meta to the hydroxygroup on each arylene group. In another embodiment, r and s is each 0.Specific examples of dihydroxy aromatic compounds of formula (VIII)include 1,1-bis(4-hydroxyphenyl) methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane(“bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane,3,3-bis(4-hydroxyphenyl)phthalimidine, and2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP).

In a specific embodiment, an impact modifier and/or an ungrafted rigidpolymer is absent from the composition used to manufacture the firstlayer. It has been found that the first layer has improved scratchresistance, in combination with improved impact properties and/orchemical resistance, when the first polycarbonate, the additionalpolycarbonate, or both comprise units derived from a bisphenolcyclohexylidene of formula (VI), specifically of formula (VII).

Specifically, the first layer can comprise a first polycarbonatecomprising units derived from monomer (II), monomer (III), and abisphenol cyclohexylidene of formula (VI), specifically of formula(VII). The Examples show that a good combination of properties isobtained when the first polycarbonate comprises units derived fromhydroquinone, methyl hydroquinone, and dimethyl bisphenol cyclohexane.Optionally, no other polymer is present in the first layer.

In another embodiment, the first layer comprises a first polycarbonatecomprising units derived from monomer (II), monomer (III), and monomer(IV), specifically a monomer of formula (V); and an additionalpolycarbonate comprising units derived from a bisphenol cyclohexylideneof formula (VI), specifically formula (VII). The additionalpolycarbonate comprises greater than or equal to 50 mole percent ofrepeat units derived from the bisphenol cyclohexylidene of formula (VI),specifically formula (VII), based on the total weight of the additionalpolycarbonate. When present, the other repeat units are derived from adihydroxy aromatic compound of formula (VIII), specifically formula (V),even more specifically bisphenol A. Alternatively, the additionalpolycarbonate is a homopolymer of dimethyl bisphenol cyclohexane. Stillmore specifically, the first polycarbonate comprises repeat unitsderived from monomer (II), monomer (III), and monomer (V); and theadditional polycarbonate is a homopolymer of repeat units derived from abisphenol cyclohexylidene of formula (VI), specifically formula (VII).The Examples show that a good combination of properties is obtained whenthe first polycarbonate comprises units derived from hydroquinone,methyl hydroquinone, and bisphenol A; and the additional polycarbonateis a homopolymer of dimethyl bisphenol cyclohexane. Optionally, the onlypolymers in the first layer are the first polycarbonate and theadditional polycarbonate.

In another embodiment, the polycarbonate compositions for use in thefirst layer comprises a blend of a first polycarbonate comprising repeatunits derived from monomer (II), monomer (III), and monomer (IV); and anadditional polycarbonate also comprising units derived from monomer(II), monomer (III), and monomer (IV). Specifically, the monomer offormula (IV) in the first polycarbonate is a monomer of formula (V), andthe monomer of formula (IV) in the additional polycarbonate is abisphenol cyclohexylidene of formula (VI) and more specifically themonomer of formula (VII). The additional polycarbonate comprises greaterthan or equal to 50 mole percent of repeat units derived from thebisphenol cyclohexylidene of formula (VI), and more specifically formula(VII), based on the total weight of the additional polycarbonate.

When blends for use in the first layer comprise a combination of thefirst polycarbonate and an additional polycarbonate, the blend comprises1 to 95 wt. % of the first polycarbonate, and 5 to 99 wt. % of theadditional polycarbonate, each based on the total weight of thepolycarbonates in the polycarbonate blend. In some embodiments, asuperior combination of mechanical, chemical, and scratch resistance isfound in formulations comprising 5 to 70 wt. % of the firstpolycarbonate (specifically wherein the first polycarbonate comprisesmonomer units derived from hydroquinone, methyl hydroquinone, andbisphenol A), and 30 to 95 wt. % of an additional polycarbonatecomprising at least 50 mole percent of units derived from a bisphenolcyclohexylidene of formula (VI), specifically dimethyl bisphenolcyclohexane. In other embodiments, superior resistance to staining orcracking after exposure to gasoline is found in formulations comprising5 to 60 wt. % of the first polycarbonate (specifically wherein the firstpolycarbonate comprises monomer units derived from hydroquinone, methylhydroquinone, and bisphenol A), and from 40 to 90 wt. % of an additionalpolycarbonate comprising at least 50 mole percent of units derived froma bisphenol cyclohexylidene of formula (VI), specifically dimethylbisphenol cyclohexane. Each of the foregoing wt. % amounts is based onthe total weight of the polycarbonates in the first layer.

The multilayer thermoplastic film comprising a first layer as describedabove (i.e., a first polycarbonate as described above or a blend of afirst polycarbonate and an additional polycarbonate) and a second layeras described below can have an advantageous combination of properties,including one or more of hardness, scratch resistance, impactperformance, and chemical resistance, in combination with one or more ofhigh light transmissivity, low haze, good Izod impact values.

A surface of the first layer of a coextruded multilayer thermoplasticfilm comprising the first polycarbonate or the polycarbonate blend canexhibit a pencil hardness of greater than or equal to HB as measuredaccording to ASTM D3363-05 using a 500 gram load. A surface of the firstlayer of the coextruded multilayer thermoplastic film can exhibit ascratch depth of less than or equal to 1.0 micrometers (μm),specifically less than or equal to 0.80 micrometers, and even less thanor equal to 0.50 micrometers, as determined using an applied force of 6N.

Use of a first layer as described above in combination with atransparent second layer can provide a multilayer film that exhibits alight transmission of greater than or equal to 60%, specifically greaterthan or equal to 70%, more specifically greater than or equal to 80%,still more specifically greater than or equal to 90%, as measured inaccordance with ASTM D1003-00 using a sample having a thickness of 0.32mm.

A coextruded multilayer film comprising the above-described first layercan have a tear initiation strength of greater than or equal to 200Newtons per millimeter (N/mm), specifically greater than or equal to 230N/mm, and more specifically greater than or equal to 280 N/mm asmeasured by ASTM D1004-03; a tear propagation strength of greater thanor equal to 8.0 N/mm, specifically greater than or equal to 10N/mm, morespecifically greater than or equal to 11 N/mm, and even morespecifically greater than or equal to 12 N/mm as measured in accordancewith D1938-02; and/or a tensile modulus of greater than or equal to2,000 megaPascals (MPa), specifically greater than or equal to 2,100MPa, and more specifically, greater than or equal to 2,200 MPa asmeasured in accordance with ISO 527.

The polycarbonate blends can have a particularly advantageouscombination of properties, including one or more of hardness, scratchresistance, and chemical resistance, in combination with one or more ofhigh light transmissivity, low haze, good impact properties. A samplecomprising the polycarbonate blend can exhibit an Izod notched impact(on a 4 mm molded sample) of at least 2.5, specifically at least 3kiloJoules per square meter (kJ/m²) as measured in accordance with ISO180-1A.

The multi-axial impact of the polycarbonate blend can be characterizedby a maximum force of 7000 to 12000 Newtons (N), an energy at maximum of20 to 100 Joules (J), an energy at break of 20 to 110 J and a deflectionat break of 6 to 20 mm, as measured on a 3.2 mm molded sample inaccordance with ISO 6603-2.

Molded samples comprising the polycarbonate blend can have a scratchresistance determined using an Erichsen Scratch Tester Type 413according to ISO 1518, by applying a force of 6 N to a conical styluswith radius of 0.01 millimeter (mm) of less than 18 micrometers, butmore specifically less than 14 micrometers, even more preferably lessthan 13 micrometers, less than 12 micrometers, or less than 10micrometers.

It has further been found by the inventors hereof that when a blend ofdifferent polycarbonates is used in the first layer, a catalyst can bepresent during the melt blending of the polycarbonate combination. Thus,also disclosed is a method of making a polycarbonate compositioncomprising melt blending a mixture comprising a first polycarbonatecomprising repeat units derived from monomers (II), (III), and (V); anadditional polycarbonate comprising greater than or equal to 50 molepercent of repeat units derived from a bisphenol cyclohexylidene offormula (VI), specifically formula (VII); and a catalyst.

Suitable catalysts are numerous and include a wide variety of bases andLewis acids. When used to make a multilayer thermoplastic film, thecatalyst is selected so as to not substantially adversely affect themanufacture or properties of the polycarbonate composition and resultingfilm.

Specific catalysts within the scope of this disclosure, i.e., thosewhich produce first layers having an improved combination of properties,include phase transfer and transesterification catalysts such as C₄-C₈₀tetraorganoammonium compounds, C₄-C₈₀ tetraorganophosphonium compounds,or a combination comprising at least one of the foregoing catalysts, inparticular ammonium and phosphonium compounds of the formula (R⁴)₄Q⁺X asdescribed above, wherein each R⁴ is independently a C₁₋₂₀ hydrocarbon; Qis a nitrogen or phosphorus atom; and X is an inorganic or C₁₋₂₀ organicanion, in particular a halogen atom, a C₁₋₈ alkoxy group, or a C₆₋₁₈aryloxy group.

Exemplary tetraorganoammonium compounds include compounds of structure(IX):

wherein R⁹ to R¹² are each independently a C₁₋₂₀ alkyl radical, C₄₋₂₀cycloalkyl radical, or a C₄₋₂₀ aryl radical, specifically wherein R⁹ toR¹² are the same C₁₋₈ alkyl radical; and X⁻ is a C₁₋₂₀ organic orinorganic anion, for example hydroxide, halide, C₁₋₂₀ carboxylate,sulfonate, sulfate, carbonate, or bicarbonate. In one embodiment, R⁹ toR¹² are the same C₁₋₈ alkyl radical, and X⁻ is a bromide, chloride,carbonate, C₁₋₆ organic ion (e.g., carboxylate, alkoxide, phenoxide orbisphenoxide), or hydroxide.

Exemplary tetraorganophosphonium compounds include compounds ofstructure (X):

wherein R⁹ to R¹² and X⁻ are as previously described. Specifically, R⁹to R¹² are the same C₁₋₈ alkyl radical, and X⁻ is a bromide, chloride,carbonate, C₁₋₆ organic ion (e.g., carboxylate, alkoxide, phenoxide, orbisphenoxide), or hydroxide.

Where X⁻ is a polyvalent anion such as carbonate or sulfate it isunderstood that the positive and negative charges in structures (VIII)and (IX) are properly balanced. For example, when R⁹ to R¹² aremonovalent alkyl groups and X⁻ is carbonate, it is understood that X⁻represents ½(CO₃ ⁻²).

The quaternary ammonium compound, quaternary phosphonium compound, orcombination thereof can optionally be used in combination with an alkalimetal and/or alkaline earth metal salt and/or hydroxide. For example,the catalyst can be a mixture of sodium hydroxide, and tetrabutylphosphonium acetate. In another embodiment, the catalyst is a mixture ofsodium hydroxide and tetramethyl ammonium hydroxide.

Specific catalysts include a tetraalkylphosphonium hydroxide,tetraalkylphosphonium carbonate, tetraalkylammonium hydroxide,tetraalkyl ammonium carbonate, tetraalkylammonium phosphate,tetraalkylammonium acetate, and combinations comprising at least one ofthe foregoing catalysts, wherein each alkyl group independently has 1 to6 carbon atoms. More specifically, the catalyst can betetramethylammonium hydroxide, tetrabutylammonium hydroxide,tetraethylammonium hydroxide, tetrabutylphosphonium acetate,tetrabutylphosphonium hydroxide, or a combination comprising at leastone of the foregoing catalysts. In one embodiment the catalyst is atetra C₁-C₁₀ alkyl phosphonium hydroxide that is decomposable underreaction conditions to very low levels of the active catalytic species.Most specifically, the catalyst is tetrabutylphosphonium hydroxide(TBPH).

The catalyst can be added in a variety of forms. The catalyst can beadded as a solid, for example as a powder, or it can be dissolved in asolvent, for example, in water or alcohol. An effective amount ofcatalyst will depend on the types and relative amounts of eachpolycarbonate and the desired properties of the first layer. Thecatalyst is present in sufficient amount to catalyze the reaction to asufficient degree to product a transparent reaction product, but is notpresent in an excessive degree, where an excess of catalyst can producean opaque reaction product. The optimal catalyst level will varydepending on the particular catalyst and can be determined by testing.In general, the catalyst is present in an amount from 0.0005 to 0.05 wt.%, based on the total weight of the polycarbonates. Specifically, thecatalyst can be present in an amount of 0.001 to 0.01 wt. %, morespecifically in an amount of 0.005 to 0.08 wt. %, more specifically0.002 to 0.07 wt. %, based on the total weight of the polycarbonates,particularly when using a tetra C₁-C₆ alkyl phosphonium hydroxide suchas tetrabutylphosphonium hydroxide.

The relative amount of the first polymer and the additional polymer inthe catalyzed blend can vary widely, and will depend on the desiredproperties of the composition. For example, the catalyzed blend cancomprise 1 to 95 wt. % of the first polycarbonate, and 5 to 99 wt. % ofthe additional polycarbonate, each based on the total weight of thepolycarbonates in the polycarbonate blend. In some embodiments, asuperior combination of chemical, impact, and scratch resistance isfound in formulations comprising 5 to 70 wt. % of the firstpolycarbonate (specifically wherein the first polycarbonate comprisesmonomer units derived from hydroquinone, methyl hydroquinone, andbisphenol A), and 30 to 95 wt. % of an additional polycarbonatecomprising at least 50 mole percent of units derived from a bisphenolcyclohexylidene of formula (VI), specifically dimethyl bisphenolcyclohexane. In other embodiments, superior resistance to staining orcracking after exposure to gasoline is found in formulations comprising5 to 60 wt. % of the first polycarbonate (specifically wherein the firstpolycarbonate comprises monomer units derived from hydroquinone, methylhydroquinone, and bisphenol A), and from 40 to 90 wt. % of an additionalpolycarbonate comprising at least 50 mole percent of units derived froma bisphenol cyclohexylidene of formula (VI), specifically dimethylbisphenol cyclohexane. Each of the foregoing wt. % amounts is based onthe total weight of the polycarbonates in the first layer.

The catalyzed reaction is generally carried out in the melt, for a timeeffective to provide a uniform dispersion having the desired properties.The temperatures and times can therefore vary depending on the identityof the polycarbonates and the properties desired. Exemplary temperaturesare 250 to 340° C., more specifically 280 to 310° C. An exemplary timeis 10 to 60 seconds. The catalyzed reaction can be convenientlyaccomplished in an extruder, reaction, vessel, or the like. In oneembodiment, in one manner of proceeding, the powdered polycarbonatesand/or other optional components are first blended, for example usinghand mixing or a Henschel™ high speed mixer. The blend is then fed intothe throat or feedthroat of a twin-screw extruder via a hopper.Alternatively, one or more of the components may be incorporated intothe composition by feeding directly into the extruder at the throatand/or downstream through a sidestuffer or feedport. Such additives mayalso be compounded into a masterbatch with a desired polymeric resin andfed into the extruder. The extruder is generally operated at atemperature higher than that necessary to cause the composition to flow.The catalyst can be fed as an aqueous solution concomitantly down thethroat of the extruder, or it can be fed using a metering pump or by acalibrated gravity fed drip. The catalyst may also be blended with thepolycarbonates in a mixer prior to extrusion. The catalyst can bediluted in water from a concentration of 50 to 1 wt. % catalyst inwater. The extrudate can be quenched in a water bath and pelletized.Such pellets can be used for subsequent molding, shaping, or forming.The foregoing melt blending process can also be used to prepare thepolycarbonate blends without the catalyst.

Using the catalyst in preparing the polycarbonate composition, certainadvantageous properties can be achieved, including one or more ofhardness, scratch resistance, and chemical resistance, in combinationwith one or more of high light transmissivity, low haze, and good impactproperties. For example, a sample molded from the catalyzedpolycarbonate blend and having a thickness of 3.2 mm has a lighttransmission of greater than 60%, specifically greater than 70%, morespecifically greater than 80% as measured by ASTM D1003-00 and a haze ofless than 73% as measured by ASTM D1003-00. Use of a first layercomprising the catalyzed blend in combination with a clear second layer(transmission greater than 90%) can provide a multilayer film thatexhibits a light transmission of greater than or equal to 60%,specifically greater than or equal to 70%, more specifically greaterthan or equal to 80%, still more specifically greater than 90%, asmeasured in accordance with ASTM D1003-00, measured using a multilayerfilm having a thickness of 0.32 mm.

A surface of a coextruded multilayer film comprising the catalyzedpolycarbonate blend can exhibit a pencil hardness of greater than orequal to 2B as measured according to ASTM D3363-05 using a 500-g load. Asurface of the first layer of the coextruded multilayer thermoplasticfilm can exhibit a scratch depth of less than or equal to 1.0micrometers (μm), specifically less than or equal to 0.80 micrometers,and even less than or equal to 0.50 micrometers, as determined using anapplied force of 6 N.

A coextruded multilayer film comprising the catalyzed polycarbonateblend can have a tear initiation strength of greater than or equal to200 Newtons per millimeter (N/mm), specifically greater than or equal to230 N/mm, and more specifically greater than or equal to 280 N/mm asmeasured by ASTM D1004-03; a tear propagation strength of greater thanor equal to 8 N/mm, specifically greater than or equal to 10 N/mm, morespecifically greater than or equal to 11 N/mm, and even greater than orequal to 12 N/mm as measured in accordance with D1938-02; and/or atensile modulus of greater than or equal to 2,000 megaPascals (MPa),specifically greater than or equal to 2,100 MPa, and more specifically,greater than or equal to 2,200 MPa as measured in accordance with ISO527.

In any of the foregoing embodiments, a variety of differentpolycarbonates can be used as the second layer of the multilayer film,wherein the second layer is disposed adjacent the first layer. Inaddition, a variety of different polycarbonates can be used as the basepolymer in the manufacture of articles using the multilayer films forin-mold decoration. The particular polycarbonate in the second layerand/or base polymer is selected based on the desired properties of themultilayer film and article formed therefrom. For example, the secondlayer and/or base polymer can comprise a polycarbonate of formula (I) inwhich great than 60 wt. % of the R¹ units are derived from a dihydroxycompound of the formula HO—R¹—OH, in particular of the formulaHO-A¹-Y¹-A²-OH wherein each of A¹ and A² is a monocyclic divalentaromatic group and Y¹ is a single bond or a bridging group having one ormore atoms that separate A¹ from A². In an exemplary embodiment, oneatom separates A¹ from A². In another exemplary embodiment, each R¹ isderived from a dihydroxy aromatic compound of formula (XI):

wherein R^(e) and R^(f) are each independently a halogen or C₁₋₁₀ alkylgroup; r and s are each independently integers of 0 to 4; and X^(c) is asingle bond or a C₁₋₁₈ bridging group connecting the twohydroxy-substituted aromatic groups, where the single bond or thebridging group and the hydroxy substituent of each C₆ arylene group aredisposed ortho, meta, or para (specifically para) to each other on theC₆ arylene group. In an embodiment, X^(c) is a single bond, —O—, —S—,—S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic group. The C₁₋₁₈ organicgroup can be cyclic or acyclic, aromatic or non-aromatic, and canfurther comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur,silicon, or phosphorous. The C₁₋₁₈ organic group can be disposed suchthat the C₆ arylene groups connected thereto are each connected to acommon alkylidene carbon or to different carbons of the C₁₋₁₈ organicgroup. Specifically, X^(c) can be a C₁₋₈ alkylidene bridging group ofthe formula —C(R^(j))(R^(k))— wherein R^(j) and R^(k) are eachindependently hydrogen or C₁₋₄ alkyl. X^(c) represents In oneembodiment, p and q is each 1, and R^(e) and R^(f) are each a C₁₋₃ alkylgroup, specifically methyl, disposed meta to the hydroxy group on eacharylene group. Specific examples of dihydroxy aromatic compounds offormula (XI) include 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, bisphenol A,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane,3,3-bis(4-hydroxyphenyl)phthalimidine, and2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP). Copolycarbonatesmanufactured from combinations comprising at least one of the dihydroxyaromatic compounds of formula (XI) can also be used.

In one specific embodiment, the polycarbonate in the second layer and/orbase polymer comprises greater than or equal to 80 wt. % of repeat unitsof bisphenol A. Alternatively, the polycarbonate in the second layer isa homopolymer of bisphenol A. In another embodiment, no units derivedfrom a bisphenol cyclohexylidene are present in the second layer. Inanother embodiment, no units derived from DMBPC are present in thesecond layer.

The polycarbonates used in the second layer and/or base polymer can havean intrinsic viscosity, as determined in chloroform at 25° C., of 0.3 to1.5 deciliters per gram (dl/gm), specifically 0.45 to 1.0 dl/gm. Thepolycarbonates can have Mw=10,000 to 200,000 Daltons, specifically20,000 to 100,000 Daltons, as measured by GPC, using a crosslinkedstyrene-divinylbenzene column and calibrated to polycarbonatereferences. GPC samples are prepared at a concentration of 1 mg per mland are eluted at a flow rate of 1.5 ml per minute.

The first and/or second layers of the multilayer thermoplastic filmand/or base polymer can further include impact modifier(s) that do notadversely affect the desired composition properties, including lighttransmission. Impact modifiers can include, for example, high molecularweight elastomeric materials derived from olefins, monovinyl aromaticmonomers, acrylic and methacrylic acids and their ester derivatives, aswell as conjugated dienes. The polymers formed from conjugated dienescan be fully or partially hydrogenated. The elastomeric materials can bein the form of homopolymers or copolymers, including random, block,radial block, graft, and core-shell copolymers. Combinations of impactmodifiers can be used. Impact modifiers, when used, can be present inamounts of 1 to 30 wt. %, based on the total weight of the polymers inthe relevant composition.

The polycarbonate compositions can include various optional additives(e.g., filler(s) and/or reinforcing agent(s)) ordinarily incorporated inpolymer compositions of this type, with the proviso that the additivesare selected so as to not significantly adversely affect the desiredproperties of the extrudable composition, for example, lighttransmission of greater than 60%. Combinations of additives can be used.Such additives can be mixed at a suitable time during the mixing of thecomponents for forming the composition. Possible optional additivesinclude antioxidants, flow aids, UV absorbers, stabilizers such as lightstabilizers and others, flame retardants, lubricants, plasticizers,colorants, including pigments and dyes, anti-static agents, metaldeactivators, and combinations comprising one or more of the foregoingadditives. Effective amounts of each of the foregoing additives areknown (e.g., from 0.001 to 10 wt. % of the total weight of thecomposition), and are selected so as to not significantly adverselyaffect the desired properties of the compositions.

The polycarbonate compositions can be used to form a variety ofarticles, including sheets. Such sheets are useful by themselves, or incombination with other layers, and can be used in articles for thetransportation and construction industry. The polycarbonate compositionscan also be used to form a multiwall sheet comprising a first sheethaving a first side and a second side, wherein the first side of thefirst sheet is disposed upon a first side of a plurality of ribs; and asecond sheet having a first side and a second side, wherein the firstside of the second sheet is disposed upon a second side of the pluralityof ribs, and where the first side of the plurality of ribs is opposed tothe second side of the plurality of ribs. The first and/or the secondsheets comprise the polycarbonate compositions.

The sheets can be formed by processes such as sheet extrusion, injectionmolding, gas-assist injection molding, extrusion molding, compressionmolding, blow molding, and combinations comprising at least one of theforegoing processes. Specific sheet extrusion processes include meltcasting, blown sheet extrusion, and calendaring. Co-extrusion andlamination processes can be used to form multilayer sheets or sheets.The sheets can alternatively be prepared by casting a solution orsuspension of the polycarbonate composition in a suitable solvent onto asubstrate, belt, or roll, followed by removal of the solvent. Single ormultiple layers of coatings can also be applied to the single ormultilayer sheets to impart additional properties such as scratchresistance, ultra violet light resistance, aesthetic appeal, and thelike. Coatings can be applied through standard application techniquessuch as rolling, spraying, dipping, brushing, flow coating, orcombinations comprising at least one of the foregoing applicationtechniques.

Further in any of the foregoing embodiments, the multilayerthermoplastic film can be formed using a continuous calendaringco-extrusion process. In such a process, first and second single screwextruders can supply polymer melts for the individual layers (i.e., thedecorative layer and any additional polymeric layers disposed on eitherside of the substrate layer) into a feed block of an extruder apparatus.A die forms a molten polymeric web that is fed to a three-rollcalendaring stack. Commonly, such a calendaring stack can comprise twoto four counter-rotating cylindrical rolls with each roll, individually,made from metal (e.g., steel) or rubber coated metal. Each roll can beheated or cooled, as is appropriate.

The molten web formed by the die can be successively squeezed betweenthe calendaring rolls. The inter-roll clearance (“nip”) through whichthe web is drawn determines the thickness of the layers.

The layers can be coextruded to form various ratios of the first layerto total thickness of the multilayer thermoplastic film. The first layercan have a thickness of 1% to 99%, specifically, 5% to 60%, morespecifically 10% to 40% of the total multilayer thermoplastic film.Generally, the overall thickness of the multilayer film can be up to andeven exceeding several millimeters. More specifically, the multilayerfilm can have a thickness (e.g., gage) of 1 mil (25.4 μm) to 500 mils(12,700 μm), more specifically, 4 mils (100 μm) to 40 mils (1016 μm),and yet more specifically, 5 mils (125 μm) to 30 mils (762 μm).

In use, a surface of one or both layers of the multilayer thermoplasticfilm can be subjected to printing with ink. In one embodiment, anexposed surface of the second layer (a surface opposite the surfaceadjacent to first layer) layer can be subsequently decorated, inparticular printed with markings such as alphanumerics, graphics,symbols, indicia, logos, aesthetic designs, multicolored regions, and acombination comprising at least one of the foregoing. In some cases, themultilayer thermoplastic film can be used solely as a protective film,without printing.

The multilayer films (with or without printing) can further be shapedinto a three-dimensional film for specific applications. Forthree-dimensional IMD pieces or parts, there are various techniques forforming three-dimensional shapes. For example, for parts having a drawdepth greater than or equal to 1 inch (2.54 centimeters (cm)),thermoforming or variations of thermoforming can be employed. Variationsinclude but are not limited to vacuum thermoforming, zero gravitythermoforming, plug assist thermoforming, snap back thermoforming,pressure assist thermoforming, and high pressure thermoforming. Forparts containing detailed alphanumeric graphics or draw depths less thanor equal to 1 inch (2.54 cm), cold forming techniques are exemplary.These include but are not limited to embossing, matched metal forming,bladder or hydro forming, pressure forming, or contact heat pressureforming.

A molded article is also disclosed herein, comprising theabove-described multilayer thermoplastic film after the film is printed(decorated) on a surface(s) thereof with a print (decoration) and bondedto an injection molded polymeric base structure. The coated multilayerpolycarbonate film can be cold formed or thermoformed into athree-dimensional shape matching the three-dimensional shape of theinjection molded polymeric base structure. While polycarbonates havebeen disclosed for use as the base polymer in the polymeric basestructure, it is to be understood that other polymers, for examplepolyesters, can alternatively be used.

Also disclosed herein is a method of molding an article, comprisingplacing the above-described decorative film into a mold, and injecting abase polymer composition into the mold cavity space behind thedecorative film, wherein the decorative film and the injection moldedbase polymer composition form a single molded part or article. Accordingto one exemplary embodiment, molded articles are prepared by: printing adecoration on a surface of a multilayer thermoplastic film (specificallyon the exposed surface of the second layer), for example by screenprinting to form a decorative film; forming and optionally trimming thedecorative film into a three-dimensional shape; fitting the decorativefilm into a mold having a surface which matches the three-dimensionalshape of the decorative film; and injecting a base polymer composition,which can be substantially transparent, into the mold cavity behind thedecorative film to produce a one-piece, permanently bondedthree-dimensional article or product.

For IMD processes, high temperature, formable inks can be used forgraphics application. Second surface decoration can employ more robustink systems to provide adequate ink adhesion during the molding process.Moreover, in applications such as light assemblies where lighttransmission is important, dye inks can be used rather than pigmentedinks so as not to affect light transmission and haze readings. Once theink is printed, it can be either dried or cured depending on the inktechnology used. If the ink is solvent or water based, then a gas firedor electric dryer can be used to dry the ink.

Among other desirable performance properties of a transparent decorativefilm and articles in which the multilayer film is contained is that itcan have a birefringence of less than or equal to 20 nm. A lowbirefringence overlay film can be used for three-dimensionalthermoformed (vacuum or pressure forming) articles prepared by IMDprocess for applications that require tight graphics registration.Various advantageous properties of the present multilayer thermoplasticfilm are described below in greater detail in the examples.

The multilayer thermoplastic polycarbonate films and decorative filmsdisclosed herein have numerous applications, for example, cell phonecovers (top, bottom, flip); cell phone lenses; cell phone key pads; lapand computer covers; key boards; membrane switches; adhesive labels;buttons and dials of interior automotive interfaces; heat ventilationand air conditioning panels; automotive clusters; control panels forappliances (washer, dryer, microwave, air conditioner, refrigerator,stove, dishwasher, etc.); housings, lenses, keypads, or covers for handheld devices (blood analyzers, calculators, MP3 or MP4 players, gamingdevices, radios, satellite radios, GPS units, etc.); touch paneldisplays; screens, keypads, membrane switches, or other user interfacesfor ATMs, voting machines, industrial equipment, and the like; housings,lenses, keypads, membrane switches, or covers for other consumer andindustrial electronic devices (TVs, monitors, cameras, video camcorders,microphones, radios, receivers, DVD players, VCRs, routers, cable boxes,gaming devices, slot machines, pachinko machines, cash registers, handheld or stationary scanners, fax machines, copiers, printers, etc);covers and buttons of memory storage devices and flash drives; coversand buttons for the mouse, blue tooth transmitters, hands free devices,headsets, earphones, speakers, etc; labels, housings, lenses, touchinterfaces for musical instruments such as electronic key boards orperiphery equipment such as amplifiers, mixers, and sound boards; anddisplays, covers, or lenses of gauges, watches, and clocks.

The invention is further illustrated by the following non-limitingexamples.

EXAMPLES

Table 1 provides the abbreviation, chemical description, and source ofthe various polymers used in the multilayer thermoplastic filmconstructions described in the examples below.

TABLE 1 Abbreviation Chemical Description Source/Vendor BPA-PCPolycarbonate homopolymer derived from SABIC Innovative Plasticsbisphenol A; Mw (PC) = 30,000 g/mol) DMBPC-PC (25K) Polycarbonatehomopolymer derived from a SABIC Innovative Plastics bisphenolcyclohexylidene of formula (VII); Mw (PC) = 24,000-26,000 g/mol, target25,000 g/mol DMBPC-PC (21K) Polycarbonate homopolymer derived from aSABIC Innovative Plastics bisphenol cyclohexylidene of formula (VII); Mw(PC) = 20,000-22,000 g/mol, target 21,000 g/mol) DMBPC-BPA Polycarbonatecopolymer derived from bisphenol SABIC Innovative Plasticscyclohexylidene of formula (VII) and bisphenol A in a mole ratio of 1:1;Mw (PC) = 23,300 g/mol Terpolymer A Polycarbonate terpolymer derivedfrom SABIC Innovative Plastics (BPA/MeHQ/HQ) bisphenol A, methylhydroquinone, and hydroquinone (BPA/MeHQ/HQ) in a mole ratio ofBPA:MeHQ:HQ of 33:33:34; Mw (PC) = 26,000 g/mol. Terpolymer BPolycarbonate terpolymer derived from a SABIC Innovative Plastics(DMBPC/MeHQ/HQ) bisphenol cyclohexylidene of formula (VII), methylhydroquinone, and hydroquinone (DMBPC/MeHQ/HQ) in mole ratio ofDMBPC:MeHQ:HQ of 33:33:34; Mw (PC) = 30,100 g/mol PCCDPoly(1,4-cyclohexylidene cyclohexane-1,4- Eastman Chemical, Kingsport,dicarboxylate) Tenn. TBPH Tetrabutylphosphonium hydroxide (40 wt. % inSachem Inc. H₂O) Mw = weight average molecular weight, as measured byGPC, based on polycarbonate (PC) standards.

Unless specifically stated to the contrary, all properties set forth inthis application were determined as set forth below.

Pencil hardness was determined according to ASTM D3363-05 with a500-gram-force (gf) load when testing the first layer of the extrudedbilayer films or with a 1 kgf load when testing molded samples.

The scratch resistance of the first layer as reported in Table 5 wasdetermined with two instruments, a custom-built scratch tester using anapplied force of 6N to form an indentation parting the surface of thesample, and a 3D Kosaka to measure the scratch depth. The extent of theindentation was measured (with a 3D Kosaka device run in 2D mode using ameasurement force of 50 milliNewtons) from the bottom of the indentationto the surface.

Scratch resistance as reported in Tables 7-9 was determined on moldedsamples using an Erichsen Scratch Tester Type 413 according to ISO 1518,by applying a force of 6 N to a conical stylus with radius of 0.01millimeter (mm), to form an indentation parting the surface of thesample. The extent of the indentation was subsequently measured by aDektak® 6M profilometer and was reported as the height of theindentation measured from the bottom of the indentation to the surface.

Tear initiation and propagation strengths in Newtons per millimeter(N/mm) were measured according to ASTM D1004-03 and D1938-02,respectively, as indicated in the Tables.

Tensile strength, which was expressed as modulus (MPa), stress at yieldand at break (MPa) and strain at yield and break (%), were determinedaccording to ISO 527 at a strain rate of 50 mm/min.

Light transmission and haze were measured in accordance with ASTM D1003-00 Procedure A with a HAZE-GUARD DUAL from BYK-Gardner, using anintegrating sphere (0°/diffuse) geometry, wherein the spectralsensitivity conforms to the CIE standard spectral value under standardlamp D65. Light transmission as reported in Table 6. was measured on a0.32 mm thick coextruded film sample. Light transmission and haze asreported in Table 7 was measured on a 3.2 millimeter (mm) thick sample.

MVR (melt volume rate) at 300° C., 1.2 kilograms (kg) and 4 minutes(min) was evaluated in accordance with ISO 1133.

Izod, notched and unnotched, were measured on molded, 3 or 4 mm thicksamples in accordance with ISO 180 under 1/A at 23° C.

Multi-axial impact properties, which are expressed as maximum force (N),energy at maximum (max) in joules (J), energy at break in joules,deflection at break in millimeters, and fracture mode (ductile orbrittle), was determined in accordance with ISO 6603-2.

Environmental stress cracking (ESCR) was performed using tensile bars.For each sample, 5 tensile bars were positioned in metal strain jigsproviding 0.5% strain. For a period of 5 minutes the bars were kept wetwith Fuel-C (50/50 volume % mixture of toluene with iso-octane(2,2,4-trimethylpentane)). After this, the bars were submerged in waterand released from the strain jig. After the bars were dried with papertowels they were stored in a polyethylene bag. The next day tensileproperties were measured in accordance with ISO 527, at 50 mm/min. Theretention of elongation, stress cracking, and visual appearance werethen evaluated.

Examples 1-4 and A-D

Bilayer thermoplastic films were prepared using varying compositions inthe first layer (Examples 1-4 and A-D in Table 2) and a bisphenol Ahomopolycarbonate in the second layer. Examples A-D are comparativeexamples. The films were prepared using coextrusion to a total gauge of10 mils (254 micrometers).

TABLE 2 Thickness of first DMBPC (Me)HQ Ex. layer (%)* Composition offirst layer (wt. %)** (wt. %)** 1 30 Terpolymer A (BPA/MeHQ/HQ) 0 53 230 Terpolymer B (DMBPC/ 53 47 MeHQ/HQ) 3 30 Terpolymer A/DMBPC-PC 50 27(25K) in a 50/50 weight ratio 4 30 Terpolymer A/DMBPC-BPA 50 5 in a10/90 weight ratio A 30 DMBPC-PC (25K) 100 0 B 30 DMBPC-PC (25K)/BPA-PCin 50 0 50/50 weight ratio C 30 DMBPC-PC/PCCD in 60/40 60 0 weight ratioD BPA-PC 0 0 *Based on total thickness **Based on total formulationweight. (Me)HQ is the total of both hydroquinone and methylhydroquinonein the formulation.

In particular, coextruded bilayer thermoplastic films having a firstlayer containing the various compositions shown in Table 2 and a secondlayer, made from a commercially available bisphenol A-basedpolycarbonate from SABIC Innovative Plastics) were made via a continuouscalendaring co-extrusion process. Co-extrusion consisted of a meltdelivery system via a set of extruders each supplying the molten polymerfor the individual layers. These melt streams were then fed into a feedblock and then a die which formed a molten polymeric web that fed a setof calendaring rolls, which opposing rolls were made from steel andrubber-covered steel and were internally heated or cooled fortemperature control. The molten web was successively squeezed betweenthese rolls. The inter-roll clearances or “nips” through which thepolymers were drawn through determined the thicknesses of the films

As an illustration, the process conditions corresponding to Sample 3 inTable 2 above are provided in Table 3. It is understood that the processwindow for extruding these films is not restricted to that illustratedin Table 3. One objective of Example 1 was to determine whether or notthere exists a condition at which these coextruded films could be made,i.e., whether or not these films are coextrudable. Thus, Table 3 belowmerely provides one set of run conditions for coextruding these films.

TABLE 3 Main Extruder diameter 1.75 inches (4.44 cm) Coextruder Diameter1.25 inches (3.18 cm) Main Extruder End Zone Temp (° F.) Zone 1/Zone2/Zone 3 485/500/515° F. (252/260/268° C.) Main Extruder Melt Temp atexit 529° F. (276° C.) Coextruder End Zone Temp (° F.) Zone 1/Zone2/Zone 3 470/485/500° F. (243/252/260° C.) Coextruded Melt Temp at exit520° F. (271° C.) RPM¹ (Main/Coex) (40.5)/49 Feedblock 525° F. (274° C.)Die Temp (° F.) (3 zones) 530°/530°/530° F. (277/277/277° C.) Roll Temp(Top/Bottom) (° F.) 210°/250° F. (99/121° C.) ¹RPM—revolutions perminute

Examples 1-4 and A-D were tested for: (1) IMD processability, (2)mechanical properties, and (3) chemical resistance. Articles suitablefor IMD applications are amenable to the three sub-processes of IMD: (a)extrudability, the ability to make films out of the selected materials,at a surface quality comparable to commercially available polishedgraphic films; (b) formability, the ability to draw the films intodifferent geometries; and (c) trimmability, the ability to cut the filmcleanly without inducing any cracking or delamination.

Examples 1-4 and A-D were evaluated for surface quality, formability,and trimmability. Results are shown in Table 4.

To measure surface quality, specimens of each of the coextruded films ofExamples 1-4 and A-D (12 inches×12 inches (30.5 cm×30.5 cm)) werevisually examined using the unaided eye to identify any grossimperfections (e.g., lines, dents, bumps) of greater than 2 mm inlength. Each specimen was rated on a scale of 1 (worst) to 5 (best).Absence, to the unaided eye, of any such imperfection was given a rating5. This evaluation was not intended to test the optical quality of thefilms, but instead to identify any gross imperfections that might ariseduring film co-extrusion. The “unaided eye” in these tests excludes theuse of optical devices for magnification with the exception ofcorrective lenses needed for normal eyesight.

To test formability, specimens of each of the coextruded films ofExamples 1-4 and A-D (12 inches×12 inches (30.5 cm×30.5 cm)) of thecoextruded film were preheated to 140° C. and then vacuum formed on aCOMET Thermoformer, with the male forming tool at 120° C., a minimumcurvature of 5 mm, and maximum draw of 10 mm. The thermoformed filmswere visually examined using the unaided eye to detect wrinkles,whitening, or tears on the film arising during the thermoformingprocess. Each specimen was rated on a scale of 1 to 5 (5 being free ofdeformations).

To test for trimmability, specimens of each of the thermoformed,coextruded films of Examples 1-4 and A-D were trimmed using matchedmetal dies comprising hardened male and female die halves (American Ironand Steel Institute “AISI” Type A2 steel), with a clearance between themale die half and female die half of 10% of sheet thickness, wherein thepart was at a 90 degree angle to the blade at the time of impact.Multilayer films with poor interlayer adhesion tend to delaminate duringthis step. The appearance of any signs of cracking or any visibledelamination during this step was also observed visually by the unaidedeye and rated on a scale of 1 to 5 (where 5 meant no defects).

TABLE 4 Attributes 1 2 3 4 A B C D Film extrudability/Surface Quality 55 5 5 5 5 5 5 Formability Rating 5 5 5 5 5 5 5 5 Trimmability Rating 5 55 5 1 3 5 5

The results in Table 4 show that overall, Examples 1-4 have comparableor improved properties compared to Examples A-B. Examples 1-4 and A-Dare both extrudable and formable, measured as described above. Examples1-4 and C-D are also highly trimmable. Neither Examples A nor B havesatisfactory trimmability. All samples had comparable transmissionvalues. Thus, blends containing either Terpolymer A or Terpolymer B, orblends of Terpolymer A with a DMBPC-PC or DMBPC-BPA would providemultilayer films with excellent properties.

Films containing Examples 1-4 and A-D were further evaluated formechanical properties, in particular pencil hardness, scratchresistance, crack resistance, tear initiation strength, and tearpropagation strength. The results of the testing are shown in Table 5.

TABLE 5 1 2 3 4 A B C D Pencil Hardness - 500 g HB H 2H H 3H H H 6BScratch Depth (μm) 0.72 0.40 0.27 0.67 0.17 0.38 0.36 1.62 TearInitiation Strength (N/mm) 237 238 290 247 235 234 223 240 TearPropagation Strength (N/mm) 12 13 9 9 8 10 12 6 Tensile Modulus (MPa)2165 2264 2286 2463 2293 2107 2181 2100

Based on the results in Table 5, it is evident that compared to ExampleD, the hardness gain in Examples 2, 3 and 4 did not compromise the tearresistance of the Examples. In terms of pencil hardness, Example 3, inparticular, was superior to Examples B and C, while Examples 2 and 4were comparable to Examples B and C. Examples 2, and 3 also exhibited ascratch depth of 0.40 micrometers or less. In view of both formabilityproperties and mechanical properties in combination, it can be seen thatthe compositions of Examples 2, 3 and 4 are superior overall. Example 1is less suitable where very good scratch resistance is desired.

Examples 1-4 and A-D were evaluated for chemical and crack resistance.In particular, A4 sized sheets of each sample were obtained. Pads (3M®)soaked in each chemical were placed near the center of the sheets. Theexposed sheet was set aside for 1 hour at 72° F. (22.2° C.), after whichthe Examples were observed, with the unaided eye, for any signs ofsolvent attack such as cracking and/or staining. The light transmissionof the 0.32 mm thick coextruded film Examples before and after chemicalexposure was determined according to ASTM D1003-00. The results areshown in Table 6.

TABLE 6 1 2 3 4 A B C D Initial light transmission 91.0 91.1 92.1 91.291.7 91.3 91.5 >90 Light Fantastik ® Spray 91.2 91.1 91.9 91.2 91.4 91.391.7 Haze Transmission Cleaner after 1 hr Coppertone ® SPF 45 91.1 90.891.6 88.8 91.2 91.4 91.9 Haze exposure Suntan Lotion Vegetable Oil 92.792.2 92.7 91.2 91.9 91.8 92.5 Haze Gasoline 91.2 91.8 91.5 84.9 CracksCracks Cracks Cracks

As seen in Table 6 above, Comparative Examples A-D suffered serioussurface damage when exposed to gasoline. In comparison, Examples 1-4 hadno cracking, and practically no change in appearance or lighttransmission. Examples 1-4 therefore have improved chemical resistanceover Examples A-D. The decrease in light transmission of Examples 1-3was less than 1%.

Examples 1-4, based on the results in Table 6 above, are excellent filmsfor IMD applications where chemical resistance is highly desirable, suchas gas pump overlays, kitchen appliances, and the like. In anadvantageous feature, the unique functionality of films IMD film lies intheir multilayer construction, which results in two surfaces withcontrasting chemical properties. For example, as illustrated by Examples1-4, the top surface of the films can be engineered to be resistant tochemicals, thereby protecting the article against solvent attack. Thebottom surface, in contrast, can be a polycarbonate amenable to partialdissolution by solvents, for example those found in commerciallyavailable ink systems, which is desirable for printing graphics in IMDapplications.

Use of the two layers as described herein further allows the propertiesof the films to be tailored to meet specific application needs. Thus,when the first layer comprises a polycarbonate having repeat unitsderived from a bisphenol cyclohexane, the resulting film has excellentscratch resistance in addition to chemical and crack resistance. Therepeat units derived from a bisphenol cyclohexylidene can be eithercopolymerized with monomers (II) and (III) (as in Terpolymer B, Example2), or blended with a copolymer comprising units derived from monomers(II), (III), and (IV), wherein monomer (IV) is not a bisphenolcyclohexylidene (as in Example 3 and 4). Terpolymer A alone (Example 1),which has no repeat units from a bisphenol cyclohexane, did not provideas much hardness as Examples 2 and 3, although superior chemical (crack)resistance was obtained. More ductile samples, thus less notch sensitivematerial should be better in ESCR as notch-sensitive materials can morequickly lead to catastrophic failure during crack propagation whenexposed to chemicals.

The contribution of units derived from the dihydroxy compounds (II) and(III) is seen in the comparisons with Examples A and B. Example A, witha first layer comprising a polycarbonate having 100% repeat unitsderived from a bisphenol cyclohexane, fails when exposed to gasoline.Example B, with a first layer comprising a polycarbonate having repeatunits derived from a bisphenol cyclohexylidene and bisphenol A, alsocracks after exposure to gasoline. Thus, the chemical resistance data inTable 6 clearly demonstrates that the presence of Terpolymer A orTerpolymer B improves chemical resistance to gasoline.

In view of the above results in Tables 4, 5, and 6, the multilayerthermoplastic films disclosed herein can achieve a superior set ofdesired properties while maintaining formability. The multilayerthermoplastic films are able to provide, in one piece at the same time,a set of properties including desired chemical and crack resistance,scratch resistance, and/or mechanical strength or robustness.

Examples 5-11

Examples 5-11 show the properties of a polycarbonate blend intended foruse as the first layer of a multilayer thermoplastic film. None of theExamples contained a catalyst during manufacture of the polycarbonateblend.

The compositions were extruded on a Krupps Werner+Pfleiderer ZSK25 twinscrew extruder (screw diameter: 25 mm) at a screw velocity of 300 rpmand melt temperature of 300° C. The obtained granulate was then moldedon an Engel 110 molding machine. Parts molded for testing included 3.2mm disks (diameter: 10 cm), and impact and tensile bars. The moldingconditions were as follows: hopper: 40° C.; zone 1: 280° C.; zone 2:290° C.; zone 3: 300° C.; die: 295° C.; mold; 80° C. The cooling timewas 20 seconds, the cycle time was 38 seconds, and the injection speedwas 25 mm/s.

Compositions and results are shown in Table 7.

TABLE 7 Components 5A* 5B* 6 7 8 9 10 11 Terpolymer A (BPA/MeHQ/HQ) (wt.%) 0 0 5 10 20 0 0 0 Terpolymer B (DMBPC/MeHQ/HQ) 0 0 0 0 0 5 10 20 (wt.%) DMBPC-BPA (wt. %) 100 0 95 90 80 95 90 80 BPA-PC (wt.. %) 0 100 — — —— — — Wt. % DMBPC in formulation 56 — 53 50 45 56 56 55 Wt. % (Me)HQ informulation 0 — 3 5 11 2 5 9 Erichsen scratch (μm) 6 N 11.9 21.5 12.312.4 12.8 12.1 11.5 11.4 Pencil Hardness test, 1 kgf H 2B H F F H H HLight Transmission (%) 90.7 90.9 90.3 89.8 88.6 90.6 90.7 90.5 Haze (%)0.7 0.4 1.8 3.1 5.2 0.7 0.7 0.6 MVR (300° C./1.2 kg/4 min) 13.1 7.0 12.712.2 11.9 12.7 13.3 13.7 Vicat B120 140 145 140 139 138 139 136 138 Izodnotched impact (kJ/m²) 5 70 5 5 6 5 5 5 Izod unnotched impact (kJ/m²)114 NB NB 194 NB 213 200 183 Multi-axial Impact Energy at Max. (J) 3 13112 65 71 3 18 4 Energy at Break (J) 3 137 12 70 73 3 19 4 Deflection atBreak (mm) 4 21 5 12 13 3 6 3 Fracture mode (D)/(B) 5xB 5xD 2xD/3xB 5xD5xD 5xB 3xD/2xB 5xB *Comparative Example

The results in Table 7 show that show that a DMBPC-BPA material shows agood scratch performance with a pencil hardness of H, but impactproperties such as Izod and multi-axial impact are poor. Addition ofeither terpolymer A or terpolymer B partly improves the impactproperties as shown by the increase in the Izod unnotched impact to morethan 120 kJ/m2, even showing a rating of NB for Examples 6 and 8.Addition of greater than 5 wt. % of Terpolymer A additionally improvesthe multi-axial ductility in blends with DMBPC-BPA demonstrated in theincrease in energy at maximum load and by an increase in the amount ofductile type failures.

For all of these blends, the scratch performance is maintained at alevel of at least F when measured at 1 kgf, making these blends verysuitable for the use in both injection mold applications as well as infilm applications that require both scratch resistance as well as animproved impact performance.

Examples 12-29

Examples 12-29 were prepared as described for examples 7-16, and showthe properties of a polycarbonate blend intended for use as the firstlayer of a multilayer thermoplastic film. None of the Examples containeda catalyst during manufacture of the polycarbonate blend. Compositionsand results are shown in Table 8.

TABLE 8 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 ComponentTerpolymer A 60 50 40 30 20 10 60 50 40 30 20 10 — — — — — —(BPA/MeHQ/HQ) (wt. %) Terpolymer B — — — — — — — — — — — — 60 50 40 3020 10 (DMBPC/ MeHQ/HQ) (wt. %) DMBPC-PC (21K) 40 50 60 70 80 90 — — — —— — — — — — — (wt. %) DMBPC-PC (25K) — — — — — — 40 50 60 70 80 90 40 5060 70 80 90 (wt. %) Wt. % DMBPC in 40 50 60 70 80 90 40 50 60 70 80 9072 76 81 86 91 95 formulation Wt. % (Me)HQ in 32 27 21 16 11 5 32 27 2116 11 5 28 24 19 14 9 5 formulation Properties Erichsen scratch 12.611.2 10.9 9.9 9.6 8.6 11.8 11.3 10.8 10.1 9.2 8.8 8.7 8.6 8.4 8.9 9.38.6 (μm) 6 N Pencil Hardness F F H H H H F H H H H H H H H H H H test, 1kgf Light Transmission 87.3 87.8 88.1 88.3 88.6 89.5 87.4 88.0 88.3 88.288.6 89.4 88.7 88.3 88.3 88.9 89.6 89.7 (%) Haze (%) 5.5 4.8 6.9 8.4 5.12.5 6.8 3.4 4.3 5.1 3.9 2.0 0.8 1.0 1.4 1.5 1.3 1.0 MVR (300° C./ 10.811.2 10.8 10.5 10.9 10.9 10.2 8.7 8.3 6.9 6.7 6.8 13.6 12.9 11.9 9.5 8.87.4 1.2 kg/4 min) Vicat B120 129 131 132 134 135 137 129 131 133 135 137138 127 128 138 134 135 137 Izod notched 7 7 51 6 5 8 7 6 6 5 5 5 7 5 63 3 3 impact (kJ/m²) Izod unnotched NB NB 217 NB 136 55 223 NB NB NB 21162 NB — 108 166 55 41 impact (kJ/m²) Multi-axial Impact Energy at Max.(J) 55 106 38 3 2 2 106 117 81 10 3 3 4 3 2 3 3 3 Energy at Break (J) 59113 39 3 2 2 115 126 88 10 3 3 4 3 2 3 3 3 Deflection at 11 16 8 2 3 316 17 13 4 3 4 3 4 3 4 4 4 Break (mm) Fracture mode 5xD 5xD 5xD 5xB 5xB5xB 5xD 5xD 5xD 1xD/ 5xB 5xB 5xB 5xB 5xB 5xB 5xB 5xB (D)/(B) 4xB NB—notbroken (at >137 kJ/m²)The results in Table 8 show that specifically adding 40-60 wt. % ofterpolymer A improves multi axial impact properties of DMBPC-PC blends.Furthermore, using higher Mw DMBPC-PC, improved impact properties areobtained than when using low Mw DMBPC-PC.

Examples 30-41

Examples 30-41 were prepared as described for examples 7-16, and showthe properties of a polycarbonate blend intended for use as the firstlayer of a multilayer thermoplastic film. A catalyst (TBPH, solutioncontains 40 wt. % TBPH in water) is present in Examples 32-41.

Properties were evaluated for each of the Examples 30-41, the results ofwhich are shown in Table 9.

TABLE 9 Components 30* 31A* 31B* 32 33 34 35 36 37 38 39 40 41Terpolymer A (BPA/ 100 0 0 50 50 50 50 60 75 90 10 25 40 MeHQ/HQ) (wt.%) DMBPC-PC (25K) 0 100 0 50 50 50 50 40 25 10 90 75 60 (wt. %) BPA-PC —— 100 — — — — — — — — — — TBPH solution (wt. %) 0 0 0 0 0.002 0.01 0.0040.004 0.004 0.004 0.004 0.004 0.004 Wt. % DMBPC in 0 100 0 50 50 50 5040 25 10 90 75 60 formulation Wt. % (Me)HQ in 53 0 0 27 27 27 27 32 4048 5 13 21 formulation Erichsen scratch 16.4 8.5 21.5 12.3 13.2 13.112.9 13.6 15.2 15.7 9.2 10.2 12.1 (μm) 6 N Light Transmission (%) 83.389.8 90.9 86.4 85.8 86.2 86.2 85.1 84 83.7 89 86.8 86.3 Haze (%) 1.1 0.70.4 7.5 5.4 2.6 5.4 6.2 4.7 1.0 4.2 5.8 6.9 MVR (300° C./ 5.8 6.9 7.014.1 13.6 20.3 14.7 18.8 17.4 14.5 9.5 10.6 13.9 1.2 kg/4 min) ESCR (50%toluene/50% Good** Cracks Crack Severe Staining Cracks Some Some Good*Good* Cracks Cracks Severe iso-octane, 5 min. in 2 in 2 staining in 8staining staining in 2 in 9 Staining 0.5% strain) seconds secondsseconds seconds seconds Vicat B120 125 139 145 132 131 130 130 129 127125 137 135 132 Izod notched impact 48 2 70 5 4 3 4 4 6 10 2 2 3 (kJ/m²)Izod unnotched impact NB 26 NB NB NB NB NB NB NB NB 33 105 NB (kJ/m²)Multi-axial Impact Energy at Max. (J) 92 3.5 131 48 31 24 32 55 73 99 33 20 Energy at Break (J) 96 4 137 50 32 25 33 56 77 104 3 3 21Deflection at Break (mm) 16 4 21 10 8 7 8 11 13 16 4 3 7 Fracture mode(D)/(B) 5xD 5xB 5xD 5xD 4xD/ 4xD/ 5xD 5xD 5xD 5xD 5xB 5xB 4xD/ 1xB 1xB1xB *Comparative Examples; **No staining or cracking to the unaided eye;NB—not broken (at >137 kJ/m²)

As can be seen from Table 9, Examples 33 and 35, comprising the catalyst(0.002 and 0.004 wt. %), exhibited less staining compared to a blendwithout the catalyst (Example 32), i.e., little or no staining versussevere staining, and no cracking, while substantially retaining many ofthe other properties. When adding too much of the catalyst (Example 34),the advantage of the improved chemical resistance may be counteracted bythe possible degradation of the polymer backbone due to the presence ofa too high level of acid.

Examples 32-38 exhibited enhanced multi-axial properties, including: (i)an energy at maximum load of greater than or equal to 20 J, specificallygreater than or equal to 70 J, and more specifically greater than orequal to 90 J; Furthermore at greater than 10 wt. % of terpolymer A, theunnotched impact improved compared to DMBPC-PC.

The foregoing Examples show generally that in a blend of two polymers,an increased amount of a HQ/MeHQ/BPA terpolymer, will improve impactproperties and chemical resistance, whereas an increased amount ofDMBPC-PC will improve hardness. Use of a catalyst such as TBPH willimprove resin compatibility, although it has been found that too high anamount will result in decreased molecular weight, which leads toincreased MVR. This would be undesirable for extrusion applications.However, materials with these high MVR could still be used for injectionmolding processes.

Ranges disclosed herein are inclusive of the recited endpoint and areindependently combinable (e.g., ranges of “up to 25 wt. %, or, morespecifically, 5 wt. % to 20 wt. %”, is inclusive of the endpoints andall values between the recited endpoints). “Combination” is inclusive ofblends, mixtures, derivatives, alloys, reaction products, and so forth.The terms “first,” “second,” and so forth, herein do not denote anyorder, quantity, or importance, but rather are used to distinguish oneelement from another, and the terms “a” and “an” do not denote alimitation of quantity, but rather denote the presence of at least oneof the referenced item. Optional” or “optionally” means that thesubsequently described event or circumstance can or cannot occur, andthat the description includes instances where the event occurs andinstances where it does not. The suffix “(s)” as used herein is intendedto include both the singular and the plural of the term that itmodifies, thereby including one or more of that term (e.g., thecolorant(s) includes one or more colorants). Reference throughout thespecification to “one embodiment”, “another embodiment”, “anembodiment”, and so forth, means that a particular element (e.g.,feature, structure, and/or characteristic) described in connection withthe embodiment is included in at least one embodiment described herein,and can or can not be present in other embodiments. In addition, it isto be understood that the described elements can be combined in anysuitable manner in the various embodiments.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. However, if a termin the present application contradicts or conflicts with a term in theincorporated reference, the term from the present application takesprecedence over the conflicting term from the incorporated reference.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A multilayer thermoplastic film comprising: a first layer comprisinga first polycarbonate that comprises repeat units derived from monomers(II), (III), and (IV), wherein monomer (II) is a first dihydroxycompound of the formula:

wherein n is 0 to 4, and R^(f1) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group; monomer (III) is asecond dihydroxy compound not the same as monomer (II) and of theformula:

wherein m is 1 to 4, and R^(f2) is a halogen, a C₁₋₁₀ hydrocarbon group,or a C₁₋₁₀ halogen-substituted hydrocarbon group; and monomer (IV) is athird dihydroxy compound of the formula:

wherein R^(a) and R^(b) are each independently a halogen or C₁₋₁₂ alkylgroup that is meta to the hydroxy group on the same aromatic ring; R^(c)and R^(d) each independently represent a C₁-C₁₂ alkyl group that isortho to the hydroxy group on the same ring; p and q are eachindependently integers of 0 to 2; v and w are each independentlyintegers 0 to 2; and X^(a) is a single bond or a bridging group; whereinthe sum of the mole percent of the repeat units derived from monomers(II) and (III) is greater than or equal to 30 mole percent, based on thetotal moles of the repeat units derived from monomers (II), (III), and(IV) in the first polycarbonate, the mole percent of the repeat unitsderived from monomer (IV) is 5 to 70 mole percent, based on the totalmoles the repeat units derived from monomers (II), (III), and (IV), andthe total wt. % of the repeat units derived from monomers (II), (III),and (IV) is greater than or equal to 80 wt. % of the firstpolycarbonate; and a second layer in contact with the first layer,wherein the second layer comprises a second polycarbonate that is notthe same as the first polycarbonate in the first layer.
 2. Themultilayer thermoplastic film of claim 1, wherein the first layerexhibits at least one of the following properties: a pencil hardness ofgreater than or equal to 2B, as measured by ASTM D3363-05, and a scratchdepth of less than or equal to 0.8 micrometers, measured using a forceof 6 N.
 3. The multilayer thermoplastic film of claim 1, wherein thefilm exhibits a light transmission of greater than or equal to 60% asmeasured by ASTM D1003-00 for a multilayer film having a thickness of0.32 mm; a tear initiation strength of greater than or equal to 235 N/mmas measured by ASTM D1004-03; a tear propagation strength of greaterthan or equal to 8.5 N/mm as measured by ASTM D1938-02; and a tensilemodulus of greater than or equal to 2000 MPa as measured by ISO
 527. 4.The multilayer thermoplastic film of claim 1, wherein the film exhibits,to the unaided eye, no cracks when exposed to gasoline for 1 hour at 22°C.
 5. The multilayer thermoplastic film of claim 1, wherein monomer (II)is hydroquinone and monomer (III) methyl hydroquinone.
 6. The multilayerthermoplastic film of claim 1, wherein the monomer (IV) is 1 to 99 molepercent of the bisphenol cyclohexylidene of formula (VI) and 1 to 99mole percent of a monomer of formula (IV) that is not the same as thebisphenol cyclohexylidene of the formula (VI).
 7. The multilayerthermoplastic film of claim 1, wherein monomer (IV) is 1 to 99 molepercent of dimethyl bisphenol cyclohexane and 1 to 99 mole percent ofbisphenol A.
 8. The multilayer thermoplastic film of claim 1, whereinmonomer (IV) is 100 mole percent of the bisphenol cyclohexylidene of theformula (VI).
 9. The multilayer thermoplastic film of claim 1, whereinmonomer (IV) is 100 mole percent of bisphenol A.
 10. The multilayerthermoplastic film of claim 1, wherein the first layer further comprisesan additional polycarbonate that is not the same as the firstpolycarbonate, wherein the additional polycarbonate comprises 50 to 100mole percent of repeat units derived from a bisphenol cyclohexane of theformula (VI):

wherein R^(c1) and R^(d1) are each independently C₁₋₁₂ alkyl, R^(c2) andR^(d2) are each independently hydrogen or C₁₋₁₂ alkyl, R^(g) is C₁₋₁₂alkyl or halogen, and t is 0 to 10; and 0 to 50 mole percent of repeatunits derived from a dihydroxy aromatic compound of formula (VIII):

wherein R^(e) and R^(f) are each independently a halogen or C₁₋₁₀ alkylgroup; r and s are each independently integers of 0 to 4; X^(a) is asingle bond or a bridging group connecting the two hydroxy-substitutedaromatic groups; and the dihydroxy aromatic compound of formula (VIII)is not the same as the bisphenol cyclohexylidene of formula (VI). 11.The multilayer thermoplastic film of claim 1, comprising 5 to 95 wt. %of the first polycarbonate and 5 to 95 wt. % of the additionalpolycarbonate, based on the total weight of first and additionalpolycarbonates.
 12. The multilayer thermoplastic film of claim 1,comprising 5 to 60 wt. % of the first polycarbonate and 40 to 95 wt. %of the additional polycarbonate, based on the total weight of first andadditional polycarbonates.
 13. The multilayer thermoplastic film ofclaim 1, comprising forming the first layer from a melt-blendedcomposition comprising the first polycarbonate, the additionalpolycarbonate, and 0.0005 wt. % to 0.05 wt. % of a catalyst, based on atotal weight of the polycarbonates in the composition.
 14. Themultilayer thermoplastic film of claim 13, wherein the first layerfurther comprises an additional polycarbonate that is not the same asthe first polycarbonate, wherein the additional polycarbonate comprises50 to 100 mole percent of repeat units derived from a bisphenolcyclohexane of the formula:

wherein R^(c1) and R^(d1) are each independently C₁₋₁₂ alkyl, R^(c2) andR^(d2) are each independently hydrogen or C₁₋₁₂ alkyl, R^(g) is C₁₋₁₂alkyl or halogen, and t is 0 to 10; and 0 to 50 mole percent of repeatunits derived from a monomer of the formula:

wherein R^(a) and R^(b) are each independently a halogen or C₁₋₁₀ alkylgroup that is meta to the hydroxy group on the same aromatic ring; p andq are each independently integers of 0 to 2; and X^(b) is a C₁₋₈alkylidene bridging group of the formula —C(R^(j))(R^(k))— wherein R^(j)and R^(k) are each independently hydrogen or C₁₄ alkyl.
 15. Themultilayer thermoplastic film of claim 14, comprising 5 to 95 wt. % ofthe first polycarbonate and 5 to 95 wt. % of the additionalpolycarbonate, based on the total weight of first and additionalpolycarbonates.
 16. The multilayer thermoplastic film of claim 14,comprising 5 to 60 wt. % of the first polycarbonate and 40 to 95 wt. %of the additional polycarbonate, based on the total weight of first andadditional polycarbonates.
 17. The multilayer thermoplastic film ofclaim 1, further comprising a printed marking.
 18. A transparentmultilayer thermoplastic film comprising: a first layer comprising of ablend comprising a first polycarbonate with an Erichsen scratch depthnot larger than 14 micrometers when measured with a 6N load inaccordance with ISO 1518, and a second polycarbonate different than thefirst polycarbonate, wherein the blend of the first and the secondpolycarbonate has an Erichsen scratch depth not larger than 18micrometers when measured with a 6N load in accordance with ISO 1518 andan energy at maximum load in a multiaxial impact test of at least 20 J,measured in accordance with ISO 6603-2; and a second layer comprising apolycarbonate comprising units derived from bisphenol A, the secondlayer being int contact with the first layer.
 19. A molded articlecomprising the multilayer thermoplastic film of claim 17, in combinationwith an injection molded polymeric base to which the film is bonded. 20.A molded article comprising the multilayer thermoplastic film of claim1, in combination with an injection molded polymeric base to which thefilm is bonded, wherein the multilayer thermoplastic film has beenformed into a non-planar three-dimensional shape matching athree-dimensional shape of the injection molded polymeric basestructure, and wherein the film further comprises a printed marking. 21.A method of molding an article, comprising placing the multilayerthermoplastic film of claim 1 into a mold, and injecting a base polymerinto a mold cavity space behind the multilayer to form a single moldedpart comprising the multilayer film and the injection molded base resin.